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United States Patent |
5,131,662
|
Pollitt
|
July 21, 1992
|
High performance one-piece golf ball
Abstract
The present invention is a composition for making a solid one-piece golf
ball and the core of a two-piece or multi-layer golf ball with a butadiene
base crosslinked by a methacrylic acid zinc salt. The resulting product is
a golf ball with outstanding performance which possesses both resilience
and durability and which can be reproduced accurately and economically.
This type of golf ball is suitable for play by tournament caliber golfers.
Inventors:
|
Pollitt; Duncan H. (Milton, FL)
|
Assignee:
|
Dunlop Slazenger Corporation (Greenville, SC)
|
Appl. No.:
|
667608 |
Filed:
|
March 7, 1991 |
Current U.S. Class: |
473/372; 260/998.14; 524/86; 524/430; 524/433; 524/442; 524/908 |
Intern'l Class: |
A63B 037/06; A63B 037/12; C08K 003/34; C08K 009/00 |
Field of Search: |
273/218,220,230
524/908,86,430,433,422
260/998.14
|
References Cited
U.S. Patent Documents
4556220 | Dec., 1985 | Tominaga et al. | 273/218.
|
4561657 | Dec., 1985 | Tominaga et al. | 524/908.
|
4715607 | Dec., 1987 | Llort et al. | 273/220.
|
4770422 | Sep., 1988 | Isaac | 273/230.
|
4838556 | Jun., 1989 | Sullivan | 524/908.
|
4844471 | Jun., 1989 | Terence et al. | 273/220.
|
4955613 | Sep., 1990 | Gendreau et al. | 524/908.
|
4971329 | Nov., 1990 | Llort et al. | 273/218.
|
Primary Examiner: Ziegler; Jacob
Attorney, Agent or Firm: Lorusso & Loud
Parent Case Text
BACKGROUND OF THE INVENTION
Cross-Reference to Related Applications
This application is a continuation-in-part of U.S. patent application Ser.
No. 07/602,053 filed Oct. 24, 1990; now abandoned, which is a file wrapper
continuation of U.S. patent application Ser. No. 07/476,166 filed Feb. 7,
1990; now abandoned.
Claims
What is claimed is:
1. A method for making an improved high performance one-piece golf ball
comprising:
(a) providing a golf ball forming composition comprising:
(i) rubber, including at least 75% by weight cis-1,4 polybutadiene; 100
parts,
(ii) methacrylic acid zinc salt in the range of 20 to 70 parts per 100
parts of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(iii) basic lead silicate in the range of 0 to 15 parts per 100 parts of
rubber,
(iv) titanium dioxide in the range of 0 to 15 parts per 100 parts of
rubber,
(v) magnesium oxide in the range of 0 to 5 parts per 100 parts of rubber,
(vi) polymerized 1,2-dihydro-2,2,4-trimethylquinoline in the range of 0 to
2 parts per 100 parts of rubber,
(vii) titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-0 in the
range of 0 to 2 parts per 100 parts of rubber,
(viii) free radical initiator in the range of 0.1 to 3 parts per 100 parts
of rubber, and
(ix) N,N-m-phenylene dimaleimide in the range of 0 to 2 parts per 100 parts
of rubber,
(b) mixing the composition of step (a) to form a reaction mixture, and
(c) molding the composition to form a golf ball.
2. The method of claim 1 wherein the methacrylic acid zinc salt (ii) has a
crosslinking energy in the order of 180 Joules per gram or greater.
3. The method of claim 1 wherein the basic lead silicate (iii) is in the
range of 5 to 15 parts per 100 parts of rubber.
4. The method of claim 1 wherein the free radical initiator (viii) is
t-butyl cumyl peroxide.
5. The method of claim 1 wherein the mixing step (b) is carried out at a
temperature in the range of 20.degree. to 150.degree. C.
6. The method of claim 1 wherein the molding step (c) is carried out at a
temperature of 175.degree. C. for 20 minutes.
7. A composition comprising:
(a) cis-1,4 polybutadiene rubber; 100 parts,
(b) methacrylic acid zinc salt in the range of 20 to 70 parts per 100 parts
of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(c) basic lead silicate in the range of 5 to 15 parts per 100 parts of
rubber,
(d) titanium dioxide in the range of 0 to 15 parts per 100 parts of rubber,
(e) magnesium oxide in the range of 0 to 5 parts per 100 parts of rubber,
(f) polymerized 1,2-dihydro-2,2,4-trimethylquinoline in the range of 0 to 2
parts per 100 parts of rubber,
(g) titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-0 in the
range of 0 to 2 parts per 100 parts of rubber,
(h) t-butyl cumyl peroxide in the range of 0.1 to 3 parts per 100 parts of
rubber, and
(i) N,N-m-phenylene dimaleimide in the range of 0 to 2 parts per 100 parts
of rubber.
8. A high performance one-piece golf ball, said ball being formed from a
composition comprising:
(a) rubber, including 75% by weight cis-1,4 polybutadiene; 100 parts,
(b) methacrylic acid zinc salt in the range of 20 to 70 parts per 100 parts
of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(c) basic lead silicate in the range of 0 to 15 parts per 100 parts of
rubber,
(d) titanium dioxide in the range of 0 to 15 parts per 100 parts of rubber,
(e) magnesium oxide in the range of 0 to 5 parts per 100 parts of rubber,
(f) polymerized 1,2-dihydro-2,2,4-trimethylquinoline in the range of 0 to 2
parts per 100 parts of rubber,
(g) titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-0 in the
range of 0 to 2 parts per 100 parts of rubber,
(h) free radical initiator in the range of 0.1 to 3 parts per 100 parts of
rubber, and
(i) N,N-m-phenylene dimaleimide in the range of 0 to 2 parts per 100 parts
of rubber.
9. The ball of claim 8 wherein the basic lead silicate is in the range of 5
to 15 parts per 100 parts of rubber.
10. The ball of claim 8 wherein the free radical initiator is t-butyl cumyl
peroxide.
11. A method for making an improved high performance one-piece golf ball
comprising:
(a) providing a golf ball forming composition comprising:
(i) rubber, including 75% by weight cis-1,4 polybutadiene; 100 parts,
(ii) methacrylic acid zinc salt in the range of 20 to 70 parts per 100
parts of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(iii) filler in the range of 0 to 15 parts per 100 parts of rubber,
(iv) polymerized 1,2-dihydro-2,2,4-trimethylquinoline in the range of 0 to
2 parts per 100 parts of rubber,
(v) titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-0 in the
range of 0 to 2 parts per 100 parts of rubber,
(vi) free radical initiator in the range of 0.1 to 3 parts per 100 parts of
rubber,
(vii) N,N-m-phenylene dimaleimide in the range of 0 to 2 parts per 100
parts of rubber,
(b) mixing the composition of step (a) to form a reaction mixture, and
(c) molding the composition to form a golf ball.
12. A composition comprising:
(a) cis-1,4 polybutadiene rubber; 100 parts,
(b) methacrylic acid zinc salt in the range of 20 to 70 parts per 100 parts
of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(c) basic lead silicate in the range of 0 to 15 parts per 100 parts of
rubber,
(d) titanium dioxide in the range of 0 to 15 parts per 100 parts of rubber,
(e) magnesium oxide in the range of 0 to 5 parts per 100 parts of rubber,
(f) polymerized 1,2-dihydro-2,2,4-trimethylquinoline in the range of 0 to 2
parts per 100 parts of rubber,
(g) titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-0 in the
range of 0 to 2 parts per 100 parts of rubber,
(h) t-butyl cumyl peroxide in the range of 0.1 to 3 parts per 100 parts of
rubber, and
(i) N,N-m-phenylene dimaleimide in the range of 0 to 2 parts per 100 parts
of rubber.
13. A method for making an improved high performance one-piece golf ball
comprising:
(a) providing a golf ball forming composition comprising:
(i) rubber, including 75% by weight cis-1,4 polybutadiene; 100 parts,
(ii) methacrylic acid zinc salt in the range of 20 to 70 parts per 100
parts of rubber, said salt being the reaction product of zinc oxide and
methacrylic acid said zinc salt being present in 10% more than the
stoichiometric amount need of zinc oxide, such reaction taking place in
the presence of oxygen to reduce polymerization, said reaction being
performed by introducing oxygen into the reaction sufficient to prevent
polymerization of the zinc salt,
(iii) filler in the range of 0 to 15 parts per 100 parts of rubber,
(iv) antioxidant in the range of 0 to 2 parts per 100 parts of rubber,
(v) coupling or dispersing agent in the range of 0 to 2 parts per 100 of
rubber,
(vi) free radical initiator in the range of 0.1 to 3 parts per 100 parts of
rubber, and
(vii) co-curing agent in the range of 0 to 2 parts per 100 parts of rubber,
(b) mixing the composition of step (a) to form a reaction mixture, and
(c) molding the composition to form a golf ball.
Description
PRIOR ART
The present invention relates to a one-piece solid golf ball.
Golf balls are classified as either wound or solid. The traditional wound
golf ball has a complex structure consisting of rubber threads wound
around the center of the ball. The process for making such a ball is
time-consuming and expensive.
Solid golf balls are classified as one-piece, two-piece or multi-layer. The
one-piece golf ball consists of a single structure, the two-piece golf
ball has a solid core covered with a cover and the multi-layer ball has
three or more layers with an intermediate layer between the core and the
cover.
There has been great technological advancement in the production of
one-piece and two-piece golf balls; however, to date there is not in
existence, a one-piece golf ball that embodies both performance and
durability characteristics suitable for use by serious golfers in
tournament play. The two-piece golf ball can be used to the satisfaction
of an average golfer; but, a professional golfer would not use this type
of ball since it lacks feel and controllability i.e. click of the ball and
the ability to control spin, particularly on approach shots. Further, a
high performance one-piece golf ball is not commercially practical in that
it has not been possible to accurately reproduce it.
Most golf balls are formed from polymerized butadiene. The polybutadiene
elastomer is crosslinked by a crosslinking agent which is a rather large
quantity of a zinc salt of acrylic or methacrylic acid. An optimal
crosslinker would increase hardness without decreasing resilience.
The zinc salts of methacrylic and acrylic acids have shown great promise as
crosslinkers for butadiene in the manufacture of solid golf balls, but so
far no suitable one-piece golf ball for play by tournament caliber golfers
has been made from these materials. Golf ball compounds crosslinked by
acrylic acid zinc salts have generally demonstrated superior
characteristics in terms of resilience but tend to be less durable. Ball
forming compounds crosslinked by methacrylic acid zinc salts produce a
ball of superior durability but at the expense of resilience. The
following discussion of prior art illustrates these points.
Tominaga et al U.S. Pat. No. 4,561,657 teaches, that an improved golf ball
can be made from a rubber composition containing zinc acrylate coated with
a fatty acid such as stearic acid whereby the golf ball exhibits proper
hardness, good impact resilience and good sound and feel when hit. Another
characteristic of this type of rubber composition is that it creates good
roll workability and dipersability of rubber additives.
Isaac et al U.S. Pat. No. 4,770,422 discloses an improved golf ball which
is durable with good playing characteristics such as good initial
velocity. The composition from which this ball is formed comprises
polybutadiene crosslinked by zinc diacrylate whereby the amount of free
radical initiator is substantially below that typically used in the past.
This free radical initiator is necessary to promote the crosslinking
reaction.
Tominaga et al U.S. Pat. No. 4,556,220 discloses a golf ball which shows
markedly superior rebound performance, durability and flight carry
characteristics. This is achieved by forming the ball from polysulfide
type compounds which regulate the molecular weight of the chains which
result from crosslinking by regulating the length of such chains.
Llort et al U.S. Pat. No. 4,714,607 teaches that a better golf ball is made
by using a small amount of zinc diacrylate to crosslink polybutadiene.
Zinc diacrylate is used as a first crosslinker and zinc dimethacrylate is
used as a second crosslinker. The result is a golf ball with higher
initial velocity and higher compression. Natural rubber can be added to
improve durability.
Reiter et al U.S. Pat. No. 4,688,801 teaches that a one-piece golf ball can
be made with improved compression and fracture strength while the desired
rebound, click and feel characteristics are maintained. This is achieved
by using a coagent comprising (i) admixture of a polyvalent metal salt of
an unsaturated acid and an organic filler or (ii) a reaction product
obtained by reaction of an unsaturated carboxylic acid with an organic
filler followed by further reaction with a polyvalent metal compound in
the presence of said unsaturated carboxylic acid where such coagent
functions as a crosslinking agent with the polybutadiene elastomer.
The above-noted prior art is directed to compositions for forming one-piece
solid golf balls as well as forming the cores of two-piece golf balls.
Likewise, the compositions of the present invention are applicable to
solid one-piece golf balls and the cores of two-piece golf balls.
SUMMARY OF THE INVENTION
The present invention is a composition for making a solid one-piece golf
ball with a butadiene base which is crosslinked by a methacrylic acid zinc
salt. The resulting product is a one-piece golf ball with outstanding
performance which possesses both resilience and durability and which can
be reproduced accurately and economically. This type of golf ball is
suitable for play by tournament caliber golfers. In addition, the material
comprising the composition can be used to form the core of a two-piece or
multi-layer golf ball.
Accordingly, a principal object of the present invention is to provide a
novel composition which will produce a superior one-piece golf ball and a
superior core for a multi-piece golf ball.
Another object of the present invention is to provide a one-piece golf ball
with outstanding resilience and durability characteristics.
Yet another object of the present invention is to provide a process for
producing one-piece golf balls which produces such balls economically and
produces balls of the same consistent quality.
Yet a further object of the present invention is to provide a composition
for producing a one-piece golf ball that is suitable for play by
tournament caliber golfers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
At the outset, the present invention is described in its broadest overall
aspects with a more detailed description following. All embodiments of the
invention involve a composition which includes a polybutadiene crosslinked
with a methacrylic acid zinc salt manufactured under the tradename Z-Max
MA. This zinc salt is present in the range of 20 to 70 parts by weight
per 100 parts of rubber to be used in formulating the solid one-piece golf
ball and the core of the two-piece golf ball. The term rubber is intended
to include a major portion of polybutadiene and may include minor portions
of other polymers such as natural rubber, polyisoprene rubber, styrene
butadiene rubber, ethylene propylene rubber and nitrile elastomers. In all
embodiments, the rubber component must include at least 75% by weight of
polybutadiene. A table of the essential ingredients and their use ranges,
in accordance with the present invention, appears below.
TABLE 1
______________________________________
PPH*
______________________________________
Essential Ingredients
Rubber 100
(at least 75% Polybutadiene by weight)
Z-Max MA.sup.1 20-70
Vul Cup R.sup.2 0.1-3
(a free radical initiator)
Optional Ingredients
Basic lead silicate 0-15
Titanium dioxide 0-15
Magnesium oxide 0-5
Agerite Resin D.sup.3 0-2
CAPOWKR 9S/H.sup.4 0-2
HVA-2.sup.5 0-2
______________________________________
*parts per 100 parts of polybutadiene
.sup.1 methacrylic acid zinc salt
.sup.2 tbutyl cumyl peroxide
.sup.3 polymerized 1,2dihydro-2,2,4-trimethylquinoline
.sup.4 titanium IV, 2propanolato, tris(dodecyl)benzene sulfonatoO
.sup.5 N,Nm-phenylene dimaleimide
The result of using the composition of the present invention in forming
golf balls is a golf ball with outstanding performance. Such golf ball's
improved characteristics include resilience, durability and economical
reproducibility.
The key feature of the present invention is the methacrylic acid zinc salt
used to crosslink the butadiene. This zinc salt is unique in that its
crosslinking energy is in the same order as the energy in commercially
acceptable zinc salt made from acrylic acid, yet the golf ball produced
from this salt cross-linked with polybutadiene is superior to commercially
available balls.
Methacrylic acid zinc salt is traditionally made by reacting methacrylic
acid with zinc oxide. In accordance with the present invention, the
reaction by which the zinc salt is produced is run in an abundance of air
with 10% more than the stoichiometric amount needed of zinc oxide. The
introduction of oxygen into the reaction prevents polymerization of the
methacrylic acid during mixing with polybutadiene rubber. Specifically,
the zinc salt and the polybutadiene are blended in a roll mill producing a
corrugated surface on one side of the product. This high radiating area
keeps the temperature down and thus delays curing until the molding step.
The temperature is preferably kept down to 75.degree. C. which is below
polymerization temperature. As a result, polymerization and curing takes
place during the molding step and not during the mixing step.
In accordance with the present invention, the methacrylic acid zinc salt is
prepared by introducing a charge of 44 pounds of zinc oxide to 85 pounds
of methacrylic acid along with 0.25 pounds of stearic acid. 20 ml. of
sulfuric acid is added as a catalyst. Prior to reaction, the zinc oxide
and the stearic acid are dispersed in a solvent which contains heptane and
1,1,1-trichloroethane in about equal parts by volume and has a specific
gravity of about 0.98. During the reaction process, the methacrylic acid
and sulfuric acid are added into a rotary vacuum drier and heated to
85.degree.-90.degree. C. The solvents including the zinc oxide are then
added to the drier. A one second blast of air is bled into the evacuated
drier system at 30 second intervals to prevent polymerization of the zinc
salt. After approximately 0.75 hours in the rotary vacuum drier, the
solvents and water of reaction are substantially removed by vacuum and the
resulting product is a solid methacrylic acid zinc salt. The zinc salt is
further dried and then reduced to particle size of 1-30 microns. This salt
is currently manufactured by Yardley Ball Corporation, Milton, Fla., under
the name Z-Max MA (Z-Max) and is referred to herein by that name.
Comparative Examples 1-6 and 8-12 further describe and define the present
invention. Z-Max, Z-Max crosslinked with polybutadiene as well as two
other commercially available salts, alone and crosslinked with
polybutadiene, were analyzed and compared. The analysis was performed by
Arthur D. Little Laboratories (ADL) of Cambridge, Mass. The salts compared
with Z-Max are Sartomer 365 manufactured under this tradename by Sartomer
Co., Inc., Exton, Pa. and ReactRite manufactured under this tradename by
Rockland React-Rite, Inc., Cartersville, Ga. Two different samples of
Z-Max were analyzed; one sample was manufactured in the old Yardley Ball
Corporation plant in Pennsylvania and the other sample was manufactured in
the new, currently operating Florida plant. The Pennsylvania sample
represents Z-Max which has aged before curing and thus golf balls produced
from it would be less resilient and thus less desirable. Z-Max should
preferably be used, i.e., cross-linked with polybutadiene, within a week
of production.
Examples 1-6 and 8-12 show that many features distinguish Z-Max and the
polybutadiene cured with it from other commercially available zinc
methacrylate. To begin with, Z-Max has a higher zinc content and fresh
Z-Max has a higher exothermic heat of polymerization. The x-ray
diffraction pattern of Z-Max shows a stronger peak between 11 and 12
degrees and the particle sizes of Z-Max are the smallest of the group
analyzed. The FTIR spectrum of Z-Max has more prominent CO crystalline
peaks and the Z-Max samples had the highest solubility in xylene. The heat
of curing is highest for the fresh Z-Max sample and polybutadiene cured
with Z-Max has the highest Shore Hardness. Finally, Z-Max samples have
lower swell indices than the other samples tested.
Examples 1-6, shown below, provide the results of: 1) elemental analysis 2)
differential scanning calorimetry 3) X-ray diffraction 4) microscopic
examination 5) Fourier
EXAMPLE 1
The analysis for zinc content in the samples was carried out by plasma
analysis. The samples were also vacuum dried and analyzed for zinc, carbon
and hydrogen at Galbraith Laboratories, Inc., (GLI) in Knoxville, Tenn.
The results are shown below. `N.A.`=Not applicable.
______________________________________
WEIGHT % ELEMENT IN ZINC SALTS
% Zn % O by
Salt GLI ADL % C % H difference
______________________________________
Theoretical Zinc
27.8 N.A. 40.8 4.3 27.2
Methacrylate
PA Z-Max 1-91
30.6 N.A 35.8 3.9 29.7
PA Z-Max 10-90
N.A. 29 37.8 4.0 29
FL Z-Max 28.2 N.A. 38.3 4.1 29.4
Sartomer 365
29.4 29 37.7 3.8 29.1
ReactRite 27.0 27 39.5 4.5 29.0
______________________________________
All samples, except ReactRite, contained more than the theoretical
proportion of zinc; especially the FL Z-Max sample. All samples,
especially the FL Z-Max, contained more than the theoretical proportion of
oxygen and less than the theoretical proportion of carbon. These results
are consistent with known addition of excess zinc oxide in the production
of Z-Max and indicate that the salts had been oxidized; especially the FL
Z-Max. In hydrogen content, the Z-Max and Sartomer samples were below that
calculated by theory, but the ReactRite hydrogen content was high. This
result suggests that ReactRite contained unreacted methacrylic acid or its
polymer.
EXAMPLE 2
The heat of reaction by thermal analysis is known in the art to correlate
with chemical reactivity in curing polybutadiene. Each sample was analyzed
using a DuPont 910 Differential Scanning Calorimeter (DSC) with a
20.degree. C./minute oven ramp, nitrogen atmosphere to 300.degree. C. in
hermetically sealed pans. Each sample showed an exothermic peak due to
heat of polymerization. The peak temperature in degrees centigrade and the
heat of polymerization in joules per gram (J/g) were recorded. The older
Z-Max sample also showed an endothermic heat of melting, apparently of a
crystalline species formed on storage. It is noted that the structure of
the cured polymer is influenced by the rate of cooling.
______________________________________
DSC RESULTS WITH ZN SALTS
Sartomer
Property/Salt
PA Z-Max FL Z-Max ReactRite
365
______________________________________
Endotherm,
28.6 J/g None None None
130.degree. C.
Exotherm, J/g
138 170 61 73.9
Peak Temp.
140 217 115 225
.degree.C.
Exotherm J/g
243 No N.A. 62.7
after
annealing at
125.degree. C.
15 min.
and slow
cooling
Peak 209 N.A. N.A. 218
Temp..degree.C.
Melted, 57.5 N.A. N.A. 70.9
Polymerized
and quench
cooled with
liquid
nitrogen J/g
Temp. Peaks
213, 248, N.A. N.A. 221
.degree.C.
260
______________________________________
EXAMPLE 3
To perform the X-ray diffraction spectroscopy, the dry powders were each
pressed in an aluminium frame. The diffraction patterns with CuK alpha
radiation show no zinc oxide left in the samples.
______________________________________
X-RAY DIFFRACTION PEAK ANGLES
Angle,
Degrees PA Z-Max FL Z-Max ReactRite
Sartomer 365
______________________________________
7.3 Strong Absent Absent Weak
9.8 Strong Strong Strong Very Strong
10.6 Medium Medium Somewhat
Very Strong
Strong
11.6 Somewhat Somewhat Weak Medium
Strong Strong
Extent of
2 3 4(Least)
1(Most)
Crystalline
Part
______________________________________
The ReactRite sample clearly has the largest amorphous phase and fewer
crystals of one of the phases shared by the other two samples. The Z-Max
and Sartomer samples appeared to contain mostly crystals and all samples
had at least four crystalline planes. The Sartomer sample had particularly
strong bands in the peaks at 9 to 10 and at 10 to 11 degrees and showed
the most complicated crystalline pattern. As a check, an X-ray spectrum
was run on a known zinc acrylate and compared to a methacrylate sample.
After treatment with ethyl alcohol, the X-ray spectra of the PA Z-Max and
the Sartomer 365 samples were shown to be similar, with strong peaks
between 9 and 10 degrees and just below 11 degrees. After alcohol
treatment, the ReactRite had only one crystalline peak just below 11
degrees and a broad amorphous peak just below that.
EXAMPLE 4
The various zinc methacrylate samples were examined under the microscope at
150 and 300 x magnification. The Z-Max particles were the smallest and
most rounded, the Sartomer particles were the largest and constituted
highly crystalline acicular flat planes. The ReactRite particles in xylene
showed birefringence, suggesting a transition between amorphous and
crystalline forms.
______________________________________
MICROSCOPICAL EXAMINATION
Sartomer
Method PA Z-Max FL Z-Max ReactRite
365
______________________________________
Microscopy
Mostly 3-10 1-5 5-25 5-200
Microns,
Up to 35 Up to
Dia. 200
Shape All Irreg. Irreg. Round & Needles
Needles
Crystals
Some particles Rectan-
crystalline & gular
amorphous or Crystal-
poorly line
crystallized Plates
______________________________________
The finer particle size of the Z-Max samples corresponds with larger
surface area for increased reactivity. The Florida Z-Max appeared to be
less completely crystalline than the Sartomer. The particle sizes of the
Z-Max were much smaller than those of the two other salts. The Sartomer
sample appeared to be highly crystalline, in agreement with x-ray
observation. The ReactRite sample had a mixture of acicular crystals and
irregular roundish amorphous-looking particles. As a check, a known
Sartomer zinc acrylate was examined microscopically and compared to
methacrylate.
EXAMPLE 5
Over 40 scans were taken with a Bio-Rad FTS spectrophotometer with the
averages used to provide results. The infrared spectra differed among the
samples, in that the Z-Max samples had an additional band at 1090
reciprocal cm where carbon-to-oxygen bonds generally appear. The Z-Max
samples also showed a greater number of crystalline peaks. The crystal
form of Z-Max is clearly different from that of the other salts analyzed.
______________________________________
RESULTS FROM INFRARED SPECTROSCOPY
CO Peaks
PA Z-Max FL Z-Max ReactRite
Sartomer 365
______________________________________
1090 CO Band CO Band No extra
No extra CO
CO
1545 Yes More Fewer Fewer
and 710
Suggesting
Crystal-
linity
______________________________________
EXAMPLE 6
Excess xylene was mixed thoroughly with a weighed sample of zinc salt. The
excess of solvent was decanted off. A heat lamp was used to evaporate
xylene from both the soluble and insoluble portions before weighing. The
weight percentages recovered (some was lost on evaporation) are given
below.
______________________________________
XYLENE SOLUBILITY
PA Z-Max FL Z-Max ReactRite
Soluble
Insoluble
Soluble Insoluble
Soluble
Insoluble
______________________________________
72 19 62 29 38 57
______________________________________
The FL Z-Max had about 10% more insoluble material than the PA Z-Max
sample. The ash contents of PA Z-Max corresponded to between 29 and 30%
zinc for both the soluble and insoluble phases. The FL Z-Max had similar
results. For ReactRite, the soluble portion ash content corresponded to
32% zinc and the insoluble portion to 26%.
At this point a discussion regarding the usual composition of the base of
the solid one-piece golf ball or the core of the two-piece golf ball is
appropriate. Such a description follows.
Butadiene rubber, that is cis-1,4 polybutadiene rubber, is the primary
elastomer component, but other elastomers may also be present in smaller
quantities. Natural rubber for example, may be added to lower modulus and
improve durability. In addition to the methacrylic acid zinc salt
constituent and the free radical or peroxide initiator, numerous other
ingredients may be incorporated into the solid ball compound. The
composition usually contains fillers such as zinc oxide, barium sulfate,
lead oxide, basic lead silicate, or the like, used singularly or in
combination, to control the weight of the ball. Other additives may
include: magnesium oxide, calcium carbonate as fillers and/or acid
acceptors; mildly reinforcing fillers and/or nucleating agents such as
silicas, carbon blacks, clays and the like; silanes and/or titanates as
bonding and/or dispersing agents; antioxidants for improving process, heat
and shelf aging properties; co-curing agents such as HVA-2, TMPTA, TMPTMA
and the like; cure modifying agents such as sulfur and sulfur bearing
compounds; granular or powdered high molecular weight polymeric materials
as impact modifiers; pigments and other ingredients for imparting various
characteristics known by those skilled in the art of rubber compounding
for golf balls.
This composition is then kneaded by a suitable kneader, mixer or blender
such as a roll mill or a Banbury mixer. Next, the rubber composition is
molded using, for instance, heat pressure molding. A one-piece golf ball
is prepared by heat-pressure molding the rubber composition into a ball
having the size suitable for a golf ball. A two-piece golf ball is
prepared by heat-pressure molding the rubber composition in a core mold
having a suitable size to form a solid core and covering the core with a
suitable cover. The cover can be prepared from compositions comprising,
for instance, an ionomer resin as a main component and optionally a filler
or coloring agent such as a titanium dioxide or zinc oxide. The solid core
is covered with two covers previously molded in the form of a
hemispherical shell and is then heat-pressure molded to fuse the two
shells together to give a finished golf ball. Injection molding is also
used to introduce the covering material around the core.
One important embodiment of the composition of the present invention
comprises high cis polybutadiene as the primary elastomer, Z-Max MA
crosslinker in the range of between 20 to 70 parts, based on 100 parts of
elastomer, basic lead silicate as filler-for-weight in the range of 5 to
15 parts, titanium dioxide pigment in the range of 0 to 15 parts,
magnesium oxide acid acceptor in the range of 0 to 5 parts, AgeRite Resin
D antioxidant in the range of 0 to 2 parts, CAPOW KR 9S/H titanate in the
range of 0 to 2 parts, Vul Cup R peroxide initiator in the range of 0.1 to
3 parts, and HVA-2 co-curing agent in the range of 0 to 2 parts. The
compound is mixed at a temperature of 20.degree. to 150.degree. C. in a
Banbury mixer or a roll mill, then molded for 20 minutes at 175.degree. C.
in a 1.727"golf ball mold.
The following is an example of the preferred embodiment.
EXAMPLE 7
______________________________________
HIGH PERFORMANCE ONE-PIECE GOLF BALL
Compound: GB-1 Parts by weight
______________________________________
Polybutadiene (high cis)
100
Z-Max MA.sup.1 48
Basic lead silicate
6
Titanium dioxide 3
Magnesium oxide 1
AgeRite Resin D.sup.2
.03
CAPOW KR 9S/H.sup.3
.20
Vul Cup R.sup.4 .53
HVA-2.sup.5 .16
Total 158.92
______________________________________
.sup.1 methacrylic acid zinc salt-Yardley Ball Corp.
.sup.2 polymerized 1,2-dihydro-2,2,4-trimethylquinoline -
R. T. Vanderbilt Company
.sup.3 titanium IV, 2-propanolato, tris-(dodecyl)benzene sulfonato-O -
Kenrich Petrochemicals, Inc.
.sup.4 t-butyl cumyl peroxide - Hercules, Inc.
.sup.5 N,N-m-phenylene dimaleimide - E. I. DuPont de Nemours & Co.,
The resulting typical ball properties are:
Shore C 93
Compression
122
COR .796.
I.V. ft/sec
254.6
Comparative Examples 8-12 which appear below show the differences between
the conventional salt-polybutadiene compositions and the
Z-Max-polybutadiene compositions. The compositions were prepared in
accordance with the teachings of the present invention. The following
analyses were performed: 1) heats of crystallizing and curing rubbers 2)
exothermic recrystallization heat of cured samples 3) Shore hardness and
4) swell index.
EXAMPLE 8
The below-listed ingredients were mixed with a Type PL-V302 Brabender
PlastiCorder, Serial Number 177518, with electrical heating, air cooling
and variable speed one horsepower Type GP 100 Drive. Titanium dioxide, an
inert pigment, was omitted to facilitate examination by infrared
spectrophotometry.
______________________________________
Grams Ingredients
______________________________________
34.5 High cis-polybutadiene from Dunlop Slazenger,
Greenville, South Carolina
0.138 AgeRite Resin D, R. T. Vanderbilt poly(trimethyl
dihydroquinoline) antioxidant
0.3485
Magnesium Oxide, to neutralize acid
0.069 Capow KR 9S/H, Kenrich Petrochemical monoalkoxy
titanate coupling agent on a hydroxylated
silicon dioxide carrier
______________________________________
These materials were mixed at a temperature in the 90.degree. to
100.degree. C. range to masticate the rubber for 11 or 12 minutes. The
mixture was then allowed to cool to about 96.degree.-108.degree. C. by
reducing the stirring speed. Next, 15.962 g of one of the four zinc salts
of methacrylic acid was added; Sartomer 365, ReactRite, PA Z-Max or FL
Z-Max. After a dozen minutes of stirring, during which time the
temperature was not allowed to exceed 113.degree. C., the stirrer was
slowed and the temperature allowed to fall to about 102.degree. C. for the
addition of the curing agents which are listed below.
______________________________________
Grams Ingredients
______________________________________
0.1242 Di Cup R from Hercules, dicumyl peroxide
0.1242 Vul Cup R from Hercules, t-butyl cumyl peroxide
0.0552 HVA-2 from DuPont, N,N'-m-phenylenebismaleimide
______________________________________
These ingredients were blended for 6 minutes with the temperature kept down
to 100.degree.-102.degree. C. to prevent premature curing. Cylindrical
moldings about 6 mm thick and 32 mm wide were produced by curing at
160.degree. C. for 20 minutes in a press at 10,000 pounds on a 4-inch ram.
The round mold was about 2 inches in outer diameter.
EXAMPLE 9
The samples in the compound with rubber were cured in the DSC and the heats
of crystallizing and curing of the rubbers were measured. This important
exothermic heat was determined at 20.degree. C./minute The preceding
crystallization exotherms were determined at both 5.degree. and 20.degree.
C.
______________________________________
DSC HEATS OF CURING AND CRYSTALLIZATION
Sartomer
Zinc Salt
PA Z-Max FL Z-Max 365 ReactRite
______________________________________
20.degree. C./Minute
Rate of Increase
Heat of 5.50 8.78 6.14 17.28
Curing J/g
Initial
Spike
Broad Second
46.21 95.80 46.93 22.96
Temper-
atures, .degree.C.
First Peak:
Onset 159.1 158.8 159.2 159.1
Peak 162.1 161.6 162.0 161.8
Second Peak:
Peak 190.4 189.5 192.2 196.4
5.degree. C./Minute
Rate of Increase
First Peak:
(at 159.degree. C.):
Heat, J/g
5.48 6.93 6.37 5.49
______________________________________
The above-shown results show that the FL Z-Max sample cured more than twice
as energetically as the Sartomer 365. The ReactRite peak was not only
smaller in area but more spread out. The heat of curing is highest for FL
Z-Max and lowest for ReactRite.
When the uncured compound is heated at 20.degree. C./minute, the heat flow
after the first peak subsides to the base line followed by an excursion to
the second peak. Because other sharp exothermic spikes occur at the same
temperature in cured rubbers as in the uncured compound, when the
temperature is increased at the same rate, the first exothermic peak is
considered due to crystal reorganization and the second to the curing
reaction. The ReactRite sample, which appeared least crystalline by
microscope and x-ray, had the largest crystallization exotherm at the
20.degree. C./minute heating rate but one of the lowest heats at the
5.degree. C./minute rate. This difference suggests that the sample is not
homogeneous.
EXAMPLE 10
The exothermic recrystallization heat of the cured samples was measured.
Since curing had been carried on for 20 minutes, the transitions in the
cured compounds as noted below are concluded to have been physical rather
than chemical. In every case, spike exotherms of the cured rubbers began
at 157.5.degree. C. and peaked at 158.degree. to 159.degree. C. When the
cured rubbers were programmed in the DSC at a 5.degree. C./minute increase
in temperature, they revealed spike exotherms at about 159.degree. C.
which are considered due to reorganization in structure.
______________________________________
EXOTHERMIC TRANSITION
Zinc Salt Exothermic Heat, J/g at 158-159.degree. C.
______________________________________
PA Z-Max 15.4
FL Z-Max 15.8
Sartomer 365
19.0
ReactRite 7.64
______________________________________
The samples were close in heat of crystallization except for cured
ReactRite which was significantly lower. This may be due to a less
desirable form of cross-linking, such as the carbon-carbon bonds formed by
peroxides, especially when zinc methacrylate is absent or less active.
EXAMPLE 11
Shore hardness measurements were performed on all samples. Each molding was
measured after aging for at least five days. The five measurements were at
least 0.5 inch in from the edge as prescribed by ASTM. Averages of the
measurements were taken and are shown below.
______________________________________
SHORE HARDNESS
Zinc Salt Hardness Readings
Average
______________________________________
PA Z-Max 49 47 50 49 51
49.2
FL Z-Max 49 52 53 51 54
51.8
Sartomer 365 47 48 48 48 48
47.8
ReactRite 26 28 26 26 26
26.4
______________________________________
It is important to note, that the Z-Max samples were harder than the other
two samples indicating a higher degree of cross-linking reaction for the
same proportion of reagent.
EXAMPLE 12
The swell index was measured for each sample. This index represents the
equilibrium weight of toluene absorbed by a cured rubber divided by the
initial weight of the rubber. For example, an uptake of 69% is a swell
index of 0.69. Parts of the moldings described above were weighed into an
excess of freshly opened scintillation grade toluene and observed over
four days of aging. Each day the swollen rubber samples were blotted and
weighed in grams. The following results may vary in the last figure due to
variability in blotting technique.
______________________________________
WEIGHTS OF POLYBUTADIENE WITH TOLUENE
Zinc Salt/days
0 1 2 3 4
______________________________________
PA Z-Max 2.267 3.652 3.693 3.755
3.828
FL Z-Max 2.281 4.534 4.752 4.752
4.708
Sartomer 365
1.992 3.989 4.136 4.243
4.291
ReactRite 2.508 5.771 5.819 5.870
5.932
______________________________________
After four days, the solvent uptake was 69 weight percent toluene for the
PA Z-Max, 106% for the FL Z-Max, 115% for Sartomer and 136% for ReactRite.
This difference indicates that the polybutadiene cured with Z-Max was more
resistant to solvent and therefore more cross-linked than the
polybutadiene cured with the other salts.
The invention may be embodied in other specific forms without departing
from the spirit or essential characteristics thereof. The present
embodiments are therefore to be considered in all respects as illustrative
and not restrictive, the scope of the invention being indicated by the
appended claims rather than by the foregoing description, and there is no
intention to exclude any equivalence thereof. Hence, it is recognized that
various modifications are possible when within the scope of the present
invention as claimed.
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